Compound, photoacid generator, and resin composition for photolithography

Abstract

To provide a solidifiable compound.SOLUTION: The compound of the present invention is represented by the following general formula (1), where R1 represents an alkylene group; R2 represents an optionally substituted alkyl group or a hydrogen atom; and Rf represents a phenyl group in which at least one hydrogen atom may be substituted with a fluorine atom; provided that R1 is a C2 or higher alkylene group, or R2 is an alkyl group substituted with an alkoxy group or a hydrogen atom.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a compound, a photoacid generator, and a resin composition for photolithography. More specifically, the present invention relates to a solidifiable compound, a nonionic photoacid generator containing the compound, and a resin composition for photolithography containing the nonionic photoacid generator. [Background technology]

[0002] Patent Document 1 discloses a photoacid generator and a resin composition for photolithography, and Patent Document 2 discloses a sulfonic acid derivative compound. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-86083 A [Patent Document 2] Special Publication No. 2017-535595 Summary of the Invention [Problem to be solved by the invention]

[0004] Compounds useful as photoacid generators contained in photolithography resin compositions and the like can be solidified to improve their purity by subsequent crystallization. However, it has been revealed that when Rf in general formula (1) of Patent Document 1 is a substituent that is not a PFAS (a general term for perfluoroalkyl compounds and polyfluoroalkyl compounds), such as a fluorophenyl group, the compound of general formula (1) does not solidify.

[0005] Therefore, an object of the present invention is to provide a solidifiable compound, a nonionic photoacid generator containing the compound, and a resin composition for photolithography containing the nonionic photoacid generator. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors have found that a compound represented by the following general formula (1) can be solidified even if Rf is not a PFAS. The present application has been completed based on such findings.

[0007] That is, the present invention provides a compound represented by the following general formula (1).

[0008] [ka]

[0009] [In formula (1), R 1 represents an alkylene group. R 2 represents an optionally substituted alkyl group or a hydrogen atom. Rf represents a phenyl group in which at least one hydrogen atom may be substituted with a fluorine atom. However, R 1 is an alkylene group having 2 or more carbon atoms, or R 2 is an alkyl group substituted with an alkoxy group or a hydrogen atom.

[0010] The compound is R 1 represents a methylene group or an ethylene group, and R 2 It is preferred that represents an alkyl group substituted with an alkoxy group.

[0011] The compound is R 1 represents an ethylene group, and R 2 It is preferable that represents an alkyl group which may be substituted with an alkoxy group, or a hydrogen atom.

[0012] In the above compound, Rf preferably represents a perfluorophenyl group.

[0013] The present invention also provides a nonionic photoacid generator (A) containing the above compound.

[0014] The present invention also provides a resin composition for photolithography (Q) containing the nonionic photoacid generator (A). Effect of the Invention

[0015] The compound of the present invention can be solidified even if Rf is not a PFAS such as a trifluoromethyl group. Therefore, the purity of the compound can be improved by crystallization, and the performance as a photoacid generator is improved. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] <Compound> The present invention provides a compound represented by the following general formula (1) (hereinafter, also referred to as the compound of the present invention).

[0017] [ka]

[0018] [In formula (1), R 1 represents an alkylene group. R 2 represents an optionally substituted alkyl group or a hydrogen atom. Rf represents a phenyl group in which at least one hydrogen atom may be substituted with a fluorine atom. However, R 1 is an alkylene group having 2 or more carbon atoms, or R 2 is an alkyl group substituted with an alkoxy group or a hydrogen atom.

[0019] R 1In the above, examples of the alkylene group include an alkylene group (methylene group) having one carbon atom, and an alkylene group having two or more carbon atoms. Examples of the alkylene group having two or more carbon atoms include a linear or branched alkylene group having 2 to 8 carbon atoms, and an alkylene group having 2 to 5 carbon atoms. Examples of the linear or branched alkylene group having 2 to 8 carbon atoms include a methylmethylene group, a dimethylmethylene group, an ethylene group, a 2-methylethylene group, a 1,2-dimethylethylene group, a trimethylene group, a 2-methyl-trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, and an octamethylene group. R 1 The alkylene group in the above formula is particularly preferably an alkylene group having 1 or 2 carbon atoms, that is, a methylene group or an ethylene group, and is most preferably an ethylene group.

[0020] R 2 The number of carbon atoms in the alkyl group in the optionally substituted alkyl group in the formula (I) is preferably 1 to 16, more preferably 1 to 8, and even more preferably 4 to 8, from the viewpoints of solidification and high purity.

[0021] Examples of the alkyl group having 1 to 16 carbon atoms include a linear alkyl group having 1 to 16 carbon atoms, a branched alkyl group having 1 to 16 carbon atoms, and a cyclic alkyl group having 3 to 16 carbon atoms.

[0022] Examples of the linear alkyl group having 1 to 16 carbon atoms include a methyl group, an ethyl group, a normal propyl group, a normal butyl group, a normal pentyl group, a normal hexyl group, a normal heptyl group, a normal octyl group, a normal nonyl group, a normal decyl group, a normal undecyl group, a normal dodecyl group, a normal tridecyl group, a normal tetradecyl group, a normal pentadecyl group, and a normal hexadecyl group.

[0023] Examples of the branched alkyl group having 1 to 16 carbon atoms include an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an isopentyl group (3-methylbutyl group), a tert-pentyl group, a neopentyl group, a 2,3-dimethylpropyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an isohexyl group (4-methylpentyl group), a 2-methylpentyl group, a 3-methylpentyl group, a hexyl group having a methyl group on the side chain such as a 2-methylhexyl group, a heptyl group having a methyl group on the side chain such as a 2-methylheptyl group, and a 2-methyloctyl group. Examples of the methyl group include an octyl group having a methyl group in the side chain, a nonyl group having a methyl group in the side chain, such as a 2-methylnonyl group, a decyl group having a methyl group in the side chain, such as a 2-methyldecyl group, an undecyl group having a methyl group in the side chain, such as a 2-methylundecyl group, a dodecyl group having a methyl group in the side chain, such as a 2-methyldodecyl group or a methylundecyl group, a tridecyl group having a methyl group in the side chain, such as a 2-methyltridecyl group, a tetradecyl group having a methyl group in the side chain, such as a 2-methyltetradecyl group, and a pentadecyl group having a methyl group in the side chain, such as a 2-methylpentadecyl group.

[0024] The cyclic alkyl group having 3 to 16 carbon atoms may be a monocyclic hydrocarbon group or a polycyclic (bridged ring) hydrocarbon group. As the monocyclic hydrocarbon group, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic hydrocarbon group, a cycloalkyl group having 6 to 16 carbon atoms is preferable, and examples thereof include an adamantyl group and an isobornyl group.

[0025] R 2 In the optionally substituted alkyl group in the above, examples of the group that can be substituted include a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a formyl group, a carboxy group, a carbamoyl group, an alkoxy group, an alkylthio group, etc., and from the viewpoint of solidification and high purity, an alkoxy group is preferable. The number of these substituents substituted may be 1 to 5, or may be 1 to 3.

[0026] The alkoxy group preferably has 1 to 16 carbon atoms, and more preferably has 1 to 5 carbon atoms.

[0027] Examples of the alkoxy group include linear or branched alkoxy groups, aryloxy groups, aryl-alkyloxy groups, and groups in which two or more of these groups are bonded. Examples of the linear or branched alkoxy group include saturated alkoxy groups such as methoxy groups, ethoxy groups, propoxy groups, isopropoxy groups, butoxy groups, isobutoxy groups, sec-butoxy groups, tert-butoxy groups, pentyloxy groups, hexyloxy groups, decyloxy groups, and dodecyloxy groups, and unsaturated alkoxy groups such as allyloxy groups. Examples of the aryloxy group include phenoxy and naphthyloxy. Examples of the aryl-alkyloxy group include alkoxy groups having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as a tolyloxy group and a benzyloxy group. Examples of the group in which two or more groups are bonded include a methoxymethoxy group, an ethoxymethoxy group, a 2-methoxyethoxy group, a 1-methoxyethoxy group, and a benzyloxymethoxy group. The alkoxy group having 1 to 16 carbon atoms may be a siloxy group having 1 to 16 carbon atoms, such as a trimethylsiloxy group, a triethylsiloxy group, a triisopropylsiloxy group, a tert-butyldimethylsiloxy group, a tert-butyldiphenylsiloxy group, etc. Among these, from the viewpoint of obtaining a product with even higher purity, a linear alkoxy group is preferred, and a methoxy group or an ethoxy group is more preferred.

[0028] The alkylthio group preferably has 1 to 16 carbon atoms, and more preferably has 1 to 5 carbon atoms.

[0029] The alkylthio group includes a linear or branched alkylthio group, an arylthio group, an aryl-alkylthio group, and a group in which two or more of these groups are bonded. The linear or branched alkylthio group includes a saturated alkylthio group such as a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, an isobutylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, an isopentylthio group, a neopentylthio group, a tert-pentylthio group, an octylthio group, a decylthio group, and a dodecylthio group, and an unsaturated alkylthio group such as an allylthio group. The arylthio group includes a phenylthio group. The aryl-alkylthio group includes an alkylthio group having a hydrocarbon group to which an aryl group and an alkyl group are bonded, such as a tosylthio group and a benzylthio group. Among them, from the viewpoint of obtaining a higher purity, a linear alkylthio group is preferable, and a methylthio group and an ethylthio group are more preferable.

[0030] R 1 and R 2 From the viewpoint of obtaining a higher purity, R 1 represents a methylene group or an ethylene group, and R 2 represents an alkyl group substituted with an alkoxy group, or R 1 represents an ethylene group, and R 2 It is preferable that represents an alkyl group which may be substituted with an alkoxy group, or a hydrogen atom.

[0031] Rf may be a phenyl group that is not substituted with a fluorine atom, or may be a phenyl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0032] Examples of the phenyl group in which at least one hydrogen atom is substituted with a fluorine atom include a monofluorophenyl group, a difluorophenyl group, a trifluorophenyl group, a tetrafluorophenyl group, and a perfluorophenyl group (pentafluorophenyl group), and particularly preferably a perfluorophenyl group (pentafluorophenyl group).

[0033] Substituent {-S(R 1 )OOR 2 From the viewpoint of ease of synthesis, the bonding position of} is preferably the 3-position.

[0034] The compound of the present invention can be solidified. For example, it can be determined that the compound of the present invention can be solidified by concentrating a solution containing the compound of the present invention, adding methanol, cooling to −25° C., and confirming that crystals are precipitated.

[0035] (Synthesis method) The compound of the present invention can be synthesized, for example, by reacting a precursor (P1) obtained by reacting hydroxy-1,8-naphthalic anhydride with a compound of the following general formula (2), or the like, with hydroxylamine, and then reacting the precursor with the corresponding benzenesulfonyl chloride.

[0036] [ka]

[0037] In the general formula (2), R 1 and R 2 is defined as in general formula (1).

[0038] The reaction conditions for the reaction of hydroxy-1,8-naphthalic anhydride with the compound of general formula (2) are -30 to 100°C for 1 to 50 hours, and it is preferable to use a reaction solvent and a base catalyst in order to complete the reaction quickly and in good yield.

[0039] The reaction solvent is not particularly limited, but is preferably acetonitrile, tetrahydrofuran, dichloromethane, chloroform, etc. As the base catalyst, for example, pyridine, methylmorpholine, dimethylaminopyridine, 2,6-lutidine, triethylamine, imidazole, DBU, sodium hydride, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc. are preferred, and are usually added in an amount of 1 to 100 mol % relative to hydroxy-1,8-naphthalic anhydride.

[0040] The molar ratio of hydroxy-1,8-naphthalic anhydride to the compound of general formula (2) is usually 1:1 to 1:4.

[0041] The compound of the present invention obtained by reacting the precursor (P1) with hydroxylamine and then reacting it with the corresponding benzenesulfonyl chloride can be purified by recrystallization from an appropriate organic solvent, if necessary.

[0042] <Non-ionic photoacid generator (A)> The compound of the present invention can be used as a nonionic photoacid generator. The nonionic photoacid generator contains at least the compound of the present invention. The nonionic photoacid generator may hereinafter be referred to as the nonionic photoacid generator (A) of the present invention. The nonionic photoacid generator (A) of the present invention may be composed of the compound of the present invention, or may contain components other than the compound of the present invention. In addition, the nonionic photoacid generator (A) of the present invention may contain only one type of the compound of the present invention, or may contain two or more types. The compound of the present invention generates a super strong acid by irradiation with light, so the nonionic photoacid generator (A) containing the compound of the present invention generates a super strong acid by irradiation with light.

[0043] The nonionic photoacid generator (A) of the present invention may be dissolved in advance in a solvent that does not inhibit the reaction, in order to facilitate dissolution in the resin composition for photolithography (Q) described below.

[0044] Examples of the solvent include carbonates (propylene carbonate, ethylene carbonate, 1,2-butylene carbonate, dimethyl carbonate, diethyl carbonate, etc.), esters (ethyl acetate, ethyl lactate, β-propiolactone, β-butyrolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, etc.), ethers (ethylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, triethylene glycol diethyl ether, tripropylene glycol dibutyl ether, etc.), and ether esters (glycol ether monoesters such as ethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether acetate (PGMEA)).

[0045] When a solvent is used, the proportion of the solvent used is preferably 15 to 1000 parts by mass, and more preferably 30 to 500 parts by mass, based on 100 parts by mass of the compound of the present invention.

[0046] <Resin composition for photolithography (Q)> The nonionic photoacid generator (A) of the present invention can be used in a resin composition for photolithography. The resin composition for photolithography contains at least the nonionic photoacid generator of the present invention. The resin composition for photolithography may hereinafter be referred to as the resin composition for photolithography (Q) of the present invention. Since the resin composition for photolithography (Q) of the present invention contains the nonionic photoacid generator (A), a difference in solubility in a developer between an exposed portion and an unexposed portion is created by performing ultraviolet irradiation and post-exposure baking (PEB). The resin composition for photolithography (Q) of the present invention may contain only one type of the nonionic photoacid generator (A) of the present invention, or may contain two or more types.

[0047] The content of the photoacid generator (particularly, the nonionic photoacid generator (A) of the present invention) in the resin composition for photolithography (Q) of the present invention is, for example, 0.3 to 5.0 mass%, preferably 0.5 to 4.5 mass%, and more preferably 1.0 to 4.0 mass%, relative to the total solid content (100 mass%) of the composition.

[0048] Examples of the photolithography resin composition (Q) of the present invention include a mixture of a negative-type chemically amplified resin (QN) and a nonionic photoacid generator (A) of the present invention, and a mixture of a positive-type chemically amplified resin (QP) and a nonionic photoacid generator (A) of the present invention.

[0049] The negative-type chemically amplified resin (QN) is composed of a phenolic hydroxyl group-containing resin (QN1) and a crosslinking agent (QN2).

[0050] The phenolic hydroxyl group-containing resin (QN1) may be a resin containing a phenolic hydroxyl group, such as novolac resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, copolymer of styrene and (meth)acrylic acid derivative, phenol-xylylene glycol condensation resin, cresol-xylylene glycol condensation resin, polyimide containing a phenolic hydroxyl group, polyamic acid containing a phenolic hydroxyl group, and phenol-dicyclopentadiene condensation resin. Among these, novolac resin, polyhydroxystyrene, copolymer of hydroxystyrene, copolymer of hydroxystyrene and styrene, copolymer of hydroxystyrene, copolymer of styrene and (meth)acrylic acid derivative, and phenol-xylylene glycol condensation resin are preferred. Note that these phenolic hydroxyl group-containing resins (QN1) may be used alone or in combination of two or more.

[0051] The novolak resin can be obtained, for example, by condensing a phenol with an aldehyde in the presence of a catalyst.

[0052] Examples of the phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, catechol, resorcinol, pyrogallol, 1-naphthol, and 2-naphthol. Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, and benzaldehyde.

[0053] Specific examples of the novolak resin include phenol / formaldehyde condensed novolak resin, cresol / formaldehyde condensed novolak resin, and phenol-naphthol / formaldehyde condensed novolak resin.

[0054] The phenolic hydroxyl group-containing resin (QN1) may contain a phenolic low molecular weight compound as a part of its components.

[0055] Examples of the phenolic low molecular weight compound include 4,4'-dihydroxydiphenylmethane, 4,4'-dihydroxydiphenyl ether, tris(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, tris(4-hydroxyphenyl)ethane, 1,3-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 1,4-bis[1-(4-hydroxyphenyl)-1-methylethyl]benzene, 4,6-bis[1-(4-hydroxyphenyl)-1-methylethyl]-1,3-dihydroxybenzene, 1,1-bis(4-hydroxyphenyl)-1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, and 4,4'-{1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene}bisphenol. These low molecular weight phenolic compounds may be used alone or in combination of two or more.

[0056] The content of this phenolic low molecular weight compound in the phenolic hydroxyl group-containing resin (QN1) is preferably 40 mass % or less, and more preferably 1 to 30 mass %, based on 100 mass % of the phenolic hydroxyl group-containing resin (QN1).

[0057] The weight average molecular weight of the phenolic hydroxyl group-containing resin (QN1) is preferably 2000 or more, more preferably 2000 to 20,000, from the viewpoints of the resolution, thermal shock resistance, thermal stability, film remaining rate, etc. of the resulting insulating film.

[0058] The content of the phenolic hydroxyl group-containing resin (QN1) in the negative-type chemically amplified resin (QN) is preferably 30 to 90 mass %, more preferably 40 to 80 mass %, when the entire composition excluding the solvent is taken as 100 mass %. When the content of the phenolic hydroxyl group-containing resin (QN1) is 30 to 90 mass %, it is preferable because the film formed using the photosensitive insulating resin composition has sufficient developability with an alkaline aqueous solution.

[0059] The crosslinking agent (QN2) may be a compound capable of crosslinking the phenolic hydroxyl group-containing resin (QN1) with the strong acid generated from the nonionic photoacid generator (A) of the present invention.

[0060] Examples of the crosslinking agent (QN2) include bisphenol A-based epoxy compounds, bisphenol F-based epoxy compounds, bisphenol S-based epoxy compounds, novolac resin-based epoxy compounds, resol resin-based epoxy compounds, poly(hydroxystyrene)-based epoxy compounds, oxetane compounds, methylol group-containing melamine compounds, methylol group-containing benzoguanamine compounds, methylol group-containing urea compounds, methylol group-containing phenol compounds, alkoxyalkyl group-containing melamine compounds, alkoxyalkyl group-containing benzoguanamine compounds, alkoxyalkyl group-containing urea compounds, alkoxyalkyl group-containing phenol compounds, carboxymethyl group-containing melamine resins, carboxymethyl group-containing benzoguanamine resins, carboxymethyl group-containing urea resins, carboxymethyl group-containing phenol resins, carboxymethyl group-containing melamine compounds, carboxymethyl group-containing benzoguanamine compounds, carboxymethyl group-containing urea compounds, and carboxymethyl group-containing phenol compounds.

[0061] Of these crosslinking agents (QN2), methylol group-containing phenol compounds, methoxymethyl group-containing melamine compounds, methoxymethyl group-containing phenol compounds, methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and acetoxymethyl group-containing phenol compounds are preferred, and methoxymethyl group-containing melamine compounds (e.g., hexamethoxymethylmelamine), methoxymethyl group-containing glycoluril compounds, methoxymethyl group-containing urea compounds, and the like are more preferred.

[0062] The content of the crosslinking agent (QN2) is usually 5 to 60 mol %, preferably 10 to 50 mol %, and more preferably 15 to 40 mol %, relative to the total acidic functional groups (100 mol %) in the phenolic hydroxyl group-containing resin (QN1), from the viewpoints of reducing the residual film rate, preventing pattern meandering and swelling, and developing properties.

[0063] The positive-type chemically amplified resin (QP) may be a protecting group-introduced resin (QP2) in which a part or all of the hydrogen atoms of the acidic functional group in an alkali-soluble resin (QP1) containing one or more acidic functional groups selected from the group consisting of phenolic hydroxyl groups, carboxyl groups, and sulfonyl groups, are substituted with an acid-dissociable group. The acid-dissociable group is a group that can dissociate in the presence of a strong acid generated from the nonionic photoacid generator (A) of the present invention. The protecting group-introduced resin (QP2) is itself insoluble or poorly soluble in alkali.

[0064] Examples of the alkali-soluble resin (QP1) include a phenolic hydroxyl group-containing resin (QP11), a carboxyl group-containing resin (QP12), and a sulfonic acid group-containing resin (QP13).

[0065] As the phenolic hydroxyl group-containing resin (QP11), those exemplified and explained as the hydroxyl group-containing resin (QN1) can be used.

[0066] The carboxy group-containing resin (QP12) includes a polymer having a carboxy group, and can be obtained, for example, by vinyl polymerization of a carboxy group-containing vinyl monomer (Ba) and, if necessary, a hydrophobic group-containing vinyl monomer (Bb).

[0067] Examples of the carboxyl group-containing vinyl monomer (Ba) include unsaturated monocarboxylic acids ((meth)acrylic acid, crotonic acid, cinnamic acid, etc.), unsaturated polyvalent (divalent to tetravalent) carboxylic acids (maleic anhydride ((anhydride)), itaconic acid, fumaric acid, citraconic acid, etc.), unsaturated polyvalent carboxylic acid alkyl esters (unsaturated polyvalent carboxylic acid alkyl esters having an alkyl group having 1 to 10 carbon atoms, such as maleic acid monoalkyl esters, fumaric acid monoalkyl esters, citraconic acid monoalkyl esters, etc.), and salts thereof (alkali metal salts such as sodium salts and potassium salts, alkaline earth metal salts such as calcium salts and magnesium salts, amine salts, ammonium salts, etc.). Among these, from the viewpoints of polymerizability and ease of availability, unsaturated monocarboxylic acids are preferred, and (meth)acrylic acid is more preferred.

[0068] Examples of the hydrophobic group-containing vinyl monomer (Bb) include (meth)acrylic acid esters (Bb1) and aromatic hydrocarbon monomers (Bb2).

[0069] Examples of the (meth)acrylic acid ester (Bb1) include alkyl (meth)acrylates having an alkyl group having 1 to 20 carbon atoms (methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, n-hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, etc.), and alicyclic group-containing (meth)acrylates (dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, isobornyl (meth)acrylate, etc.).

[0070] Examples of the aromatic hydrocarbon monomer (Bb2) include hydrocarbon monomers having a styrene skeleton (styrene, α-methylstyrene, vinyltoluene, 2,4-dimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, phenylstyrene, cyclohexylstyrene, benzylstyrene, etc.) and vinylnaphthalene.

[0071] In the carboxy group-containing resin (QP12), the charged monomer molar ratio of (Ba) / (Bb) is usually 10 to 100 / 0 to 90, preferably 10 to 80 / 20 to 90, and more preferably 25 to 85 / 15 to 75 from the viewpoint of developability.

[0072] As the sulfonic acid group-containing resin (QP13), a polymer having a sulfonic acid group can be used. For example, it can be obtained by vinyl polymerization of a sulfonic acid group-containing vinyl monomer (Bc) and, if necessary, the hydrophobic group-containing vinyl monomer (Bb).

[0073] Examples of the sulfonic acid group-containing vinyl monomer (Bc) include vinyl sulfonic acid, (meth)allyl sulfonic acid, styrene sulfonic acid, α-methylstyrene sulfonic acid, 2-(meth)acryloylamide-2-methylpropane sulfonic acid, and salts thereof. Examples of the salts include alkali metal salts (such as sodium salts and potassium salts), alkaline earth metal salts (such as calcium salts and magnesium salts), primary to tertiary amine salts, ammonium salts, and quaternary ammonium salts.

[0074] In the sulfonic acid group-containing resin (QP13), the charged monomer molar ratio of (Bc) / (Bb) is usually 10 to 100 / 0 to 90, preferably 10 to 80 / 20 to 90, and more preferably 25 to 85 / 15 to 75 from the viewpoint of developability.

[0075] The HLB value of the alkali-soluble resin (QP1) preferably varies depending on the resin skeleton of the alkali-soluble resin (QP1), but is preferably 4 to 19, more preferably 5 to 18, and particularly preferably 6 to 17. If the HLB value is 4 or more, the developability is further improved when developing, and if it is 19 or less, the water resistance of the cured product is further improved.

[0076] Note that the HLB value in this specification is the HLB value determined by the Oda method, which is the hydrophilic-hydrophobic balance value and can be calculated from the ratio of the organic value and the inorganic value of the organic compound. <HLB Evaluation Method> HLB≒10×inorganic / organic

[0077] In addition, the inorganic and organic values ​​are described in detail on page 501 of the literature "Synthesis of Surfactants and Their Applications" (published by Maki Shoten, written by Oda and Teramura); or on page 198 of "New Introduction to Surfactants" (written by Takehiko Fujimoto, published by Sanyo Chemical Industries, Ltd.).

[0078] Examples of the acid-dissociable group in the protecting group-introduced resin (QP2) include a substituted methyl group, a 1-substituted ethyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, a cyclic acid-dissociable group, etc. These may be used alone or in combination of two or more.

[0079] Examples of the substituted methyl group include a methoxymethyl group, a methylthiomethyl group, an ethoxymethyl group, an ethylthiomethyl group, a methoxyethoxymethyl group, a benzyloxymethyl group, a benzylthiomethyl group, a phenacyl group, a bromophenacyl group, a methoxyphenacyl group, a methylthiophenacyl group, an α-methylphenacyl group, a cyclopropylmethyl group, a benzyl group, a diphenylmethyl group, a triphenylmethyl group, a bromobenzyl group, a nitrobenzyl group, a methoxybenzyl group, a methylthiobenzyl group, an ethoxybenzyl group, an ethylthiobenzyl group, a piperonyl group, a methoxycarbonylmethyl group, an ethoxycarbonylmethyl group, an n-propoxycarbonylmethyl group, an i-propoxycarbonylmethyl group, an n-butoxycarbonylmethyl group, and a tert-butoxycarbonylmethyl group.

[0080] Examples of the 1-substituted ethyl group include a 1-methoxyethyl group, a 1-methylthioethyl group, a 1,1-dimethoxyethyl group, a 1-ethoxyethyl group, a 1-ethylthioethyl group, a 1,1-diethoxyethyl group, a 1-ethoxypropyl group, a 1-propoxyethyl group, a 1-cyclohexyloxyethyl group, a 1-phenoxyethyl group, a 1-phenylthioethyl group, a 1,1-diphenoxyethyl group, a 1-benzyloxyethyl group, a 1-benzylthioethyl group, a 1-cyclopropylethyl group, a 1-phenylethyl group, a 1,1-diphenylethyl group, a 1-methoxycarbonylethyl group, a 1-ethoxycarbonylethyl group, a 1-n-propoxycarbonylethyl group, a 1-isopropoxycarbonylethyl group, a 1-n-butoxycarbonylethyl group, and a 1-tert-butoxycarbonylethyl group.

[0081] Examples of the 1-branched alkyl group include an isopropyl group, a sec-butyl group, a tert-butyl group, a 1,1-dimethylpropyl group, a 1-methylbutyl group, and a 1,1-dimethylbutyl group.

[0082] Examples of the silyl group include tricarbylsilyl groups such as a trimethylsilyl group, an ethyldimethylsilyl group, a diethylmethylsilyl group, a triethylsilyl group, an isopropyldimethylsilyl group, a diisopropylmethylsilyl group, a triisopropylsilyl group, a tert-butyldimethylsilyl group, a di-tert-butylmethylsilyl group, a tri-tert-butylsilyl group, a dimethylphenylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.

[0083] Examples of the germyl group include tricarbylgermyl groups such as a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an isopropyldimethylgermyl group, a methyldiisopropylgermyl group, a triisopropylgermyl group, a tert-butyldimethylgermyl group, a di-tert-butylmethylgermyl group, a tri-tert-butylgermyl group, a dimethylphenylgermyl group, a methyldiphenylgermyl group, and a triphenylgermyl group.

[0084] Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, and a tert-butoxycarbonyl group.

[0085] Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, a heptanoyl group, a hexanoyl group, a valeryl group, a pivaloyl group, an isovaleryl group, a lauroyl group, a myristoyl group, a palmitoyl group, a stearoyl group, an oxalyl group, a malonyl group, a succinyl group, a glutaryl group, an adipoyl group, a piperoyl group, a suberoyl group, an azelaoyl group, a sebacoyl group, an acryloyl group, and a propioloyl group. , methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, campholoyl group, benzoyl group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, isonicotinoyl group, p-toluenesulfonyl group, and mesyl group.

[0086] Examples of the cyclic acid-dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, a tetrahydrothiofuranyl group, a 3-bromotetrahydropyranyl group, a 4-methoxytetrahydropyranyl group, a 4-methoxytetrahydrothiopyranyl group, and a 3-tetrahydrothiophene-1,1-dioxide group.

[0087] Of these acid-dissociable groups, tert-butyl, benzyl, 1-methoxyethyl, 1-ethoxyethyl, trimethylsilyl, tert-butoxycarbonyl, tert-butoxycarbonylmethyl, tetrahydropyranyl, tetrahydrofuranyl, tetrahydrothiopyranyl, and tetrahydrothiofuranyl groups are preferred.

[0088] The introduction rate of the acid-dissociable group in the protecting group-introduced resin (QP2) {the ratio of the number of acid-dissociable groups to the total number of unprotected acidic functional groups and acid-dissociable groups in the protecting group-introduced resin (QP2)} cannot be generally defined depending on the type of acid-dissociable group and the alkali-soluble resin into which the group is introduced, but is preferably 10 to 100%, more preferably 15 to 100%.

[0089] The weight average molecular weight (hereinafter, referred to as "Mw") of the protecting group-introduced resin (QP2) in terms of polystyrene measured by gel permeation chromatography (GPC) is preferably from 1,000 to 150,000, and more preferably from 3,000 to 100,000.

[0090] The ratio (Mw / Mn) of the Mw of the protecting group-introduced resin (QP2) to the polystyrene-equivalent number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC) is usually 1 to 10, and preferably 1 to 5.

[0091] The content of the nonionic photoacid generator (A) of the present invention based on the mass (100 mass%) of the solid content of the resin composition for photolithography (Q) of the present invention is preferably 0.001 to 20 mass%, more preferably 0.01 to 15 mass%, and particularly preferably 0.05 to 7 mass%. If it is 0.001 mass% or more, the sensitivity to ultraviolet light can be more excellent, and if it is 20 mass% or less, the physical properties of the part insoluble in an alkaline developer can be more excellent.

[0092] A resist using the resin composition for photolithography (Q) of the present invention can be formed, for example, by applying a resin solution dissolved in a predetermined organic solvent (dissolved and dispersed when inorganic fine particles are contained) to a substrate by a known method such as spin coating, curtain coating, roll coating, spray coating, or screen printing, and then drying the solvent by heating or blowing hot air.

[0093] Examples of organic solvents that dissolve the resin composition for photolithography (Q) of the present invention include those that can dissolve the resin composition and can adjust the physical properties (such as viscosity) of the resin solution so that it can be applied to spin coating, etc. For example, known solvents such as N-methylpyrrolidone, DMF, dimethyl sulfoxide, toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, and xylene can be used.

[0094] Among these solvents, those having a boiling point of 200° C. or less (toluene, ethanol, cyclohexanone, methanol, methyl ethyl ketone, ethyl acetate, butyl acetate, ethyl lactate, propylene glycol monomethyl ether acetate, acetone, and xylene) are preferred from the viewpoint of drying temperature, etc. The solvents may be used alone or in combination of two or more.

[0095] When an organic solvent is used, the amount of the organic solvent is not particularly limited, but is usually preferably 30 to 1,000 parts by mass, more preferably 40 to 900 parts by mass, and particularly preferably 50 to 800 parts by mass, based on the mass (100 parts by mass) of the solid content of the resin composition for photolithography (Q) of the present invention.

[0096] The drying conditions for the resin solution after application vary depending on the solvent used, but are preferably carried out at 50 to 200°C for 2 to 30 minutes, and are appropriately determined based on the amount of residual solvent (mass%) in the resin composition for photolithography (Q) of the present invention after drying.

[0097] After forming a resist on a substrate, the resist is irradiated with light in the shape of a wiring pattern, followed by post-exposure baking (PEB) and alkaline development to form a wiring pattern.

[0098] The light irradiation method may be a method of exposing the resist to active light through a photomask having a wiring pattern. The active light used for the light irradiation may be one that decomposes the nonionic photoacid generator (A) of the present invention in the resin composition for photolithography (Q) of the present invention.

[0099] Examples of actinic rays include low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halogen lamps, electron beam irradiation devices, X-ray irradiation devices, lasers (argon lasers, dye lasers, nitrogen lasers, LEDs, helium cadmium lasers, etc.), etc. Among these, high-pressure mercury lamps and ultra-high-pressure mercury lamps are preferred.

[0100] The temperature of post-exposure bake (PEB) is usually 40 to 200°C, preferably 50 to 190°C, and more preferably 60 to 180°C. If it is 40°C or higher, the deprotection reaction or crosslinking reaction can be sufficiently carried out, and the difference in solubility between the UV-irradiated part and the UV-unirradiated part is large, making it easy to form a pattern, while if it is 200°C or lower, productivity is improved. The heating time is usually 0.5 to 120 minutes. If it is 0.5 minutes or more, the time and temperature can be easily controlled, and if it is 120 minutes or less, productivity is improved.

[0101] An example of the alkaline development method is a method of dissolving and removing the wiring pattern shape using an alkaline developer. As the alkaline developer, one that can cause a difference in solubility between the ultraviolet irradiated portion and the ultraviolet unirradiated portion of the photolithography resin composition (Q) of the present invention can be used. Examples of the alkaline developer include an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, sodium bicarbonate, and an aqueous tetramethylammonium salt solution. A water-soluble organic solvent may be added to these alkaline developers. Examples of the water-soluble organic solvent include methanol, ethanol, isopropyl alcohol, THF, and N-methylpyrrolidone.

[0102] The developing method includes a dip method, a shower method, and a spray method using an alkaline developer, and the spray method is preferred. The temperature of the developer is preferably 25 to 40° C. The developing time is appropriately determined depending on the thickness of the resist. EXAMPLES

[0103] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In the following, unless otherwise specified, % means % by mass and parts means parts by mass.

[0104] <Example 1> In a triangular flask, 21 parts of 4-bromo-1,8-naphthalic anhydride (manufactured by Tokyo Chemical Industry Co., Ltd.) and 27 parts of potassium carbonate as a base catalyst were dispersed in 400 parts of acetonitrile as a reaction solvent, and then 30 parts of methoxybutyl thioglycolate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and the mixture was allowed to react at 75°C for 6 hours. Next, potassium carbonate was removed by filtration, and 18 parts of 50% aqueous hydroxylamine solution (Tokyo Chemical Industry Co., Ltd.) was added dropwise and reacted at room temperature for 2 hours. After the reaction was completed, the reaction solution was added to ion-exchanged water, and then hydrochloric acid was added until the pH reached 5. After stirring for a while, the precipitate was collected by filtration and dried under reduced pressure at 70°C to obtain a pale yellow solid precursor. The dried precursor was dissolved in 500 parts of dichloromethane and 20 parts of pyridine, and then cooled to 10°C, and 42 parts of pentafluorobenzenesulfonyl chloride was added dropwise to the solution. After the dropwise addition, the solution was reacted at room temperature for 1 hour, and then washed with ion-exchanged water to obtain a reaction liquid.

[0105] <Example 2> The same procedure as in Example 1 was carried out, except that methoxybutyl thioglycolate was replaced with methoxybutyl mercaptopropionate.

[0106] <Example 3> The same procedure as in Example 1 was carried out, except that methoxybutyl thioglycolate was replaced with octyl mercaptopropionate.

[0107] <Example 4> The same procedure as in Example 1 was carried out, except that methoxybutyl thioglycolate was replaced with 3-mercaptopropionic acid.

[0108] 1 H-NMR and 19 The structures of the compounds contained in the reaction solutions of Examples 1 to 4 were identified as follows by F-NMR.

[0109] [ka]

[0110] Compounds contained in the reaction mixtures of Examples 1 to 4 1 H-NMR data and 19 F-NMR is as follows: Example 1 · 1 H-NMR (400MHz, solvent: deuterated chloroform), δ(ppm): 8.65(m,2H), 8.45(d,1H), 7.82(t,1H), 7.67( d,1H), 4.25(t,2H), 3.93(s,2H), 3.31(m,1H), 3.22(s,3H), 1.75(m,2H), 1.09(d,3H) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 2 · 1 H-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): 8.60 (m, 2H), 8.45 (d, 1H), 7.78 (t, 1H), 7.58 (d, 1H), 4.22(t,2H), 3.45(t,2H), 3.39(m,1H), 3.28(s,3H), 2.79(t,2H), 1.75(m,2H), 1.13(d,3H) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 3 · 1 H-NMR (400MHz, solvent: deuterated chloroform), δ(ppm): 8.62(m,2H), 8.45(d,1H), 7.78(t,1H), 7.60(d ,1H), 4.05(m,2H), 3.45(t,2H), 2.79(t,2H), 1.35(m,2H), 1.25(bs,7H), 0.85(m,6H) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Example 4 · 1 H-NMR (400MHz, solvent: deuterated chloroform), δ(ppm): 8.90(s,1H), 8.62(m,2H), 8.45(d,1H), 7.78(t,1H), 7.60(d,1H), 3.45(t,2H), 2.80(t,2H) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F)

[0111] <Comparative Example 1> The same procedure as in Example 1 was carried out, except that methoxybutyl thioglycolate was replaced with octyl thioglycolate.

[0112] <Reference example 1> The same procedure as in Example 1 was carried out, except that methoxybutyl thioglycolate was replaced with methoxybutyl mercaptopropionate, and pentafluorobenzenesulfonyl chloride was replaced with trifluoromethanesulfonic anhydride (EF-18, manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.).

[0113] 1 H-NMR and 19 The structures of the compounds contained in the reaction solutions of Comparative Example 1 and Reference Example 1 were identified as follows by F-NMR.

[0114] [ka]

[0115] H of the compounds contained in the reaction mixtures of Comparative Example 1 and Reference Example 1 1 -NMR data and 19 F-NMR is as follows: Comparative Example 1 · 1 H-NMR (400MHz, solvent: deuterated chloroform), δ(ppm): 8.63(dd,2H), 8.45(d,1H), 7.81(t,1H), 7.65( d,1H), 4.05(m,2H), 3.95(s,2H), 3.39(d,2H), 1.75(m,1H), 1.25(m,8H), 0.85(m,3H) · 19 F-NMR (400 MHz, solvent: deuterated chloroform), δ (ppm): -132.5 (m, 2F), -141.6 (m, 1F), -158.0 (m, 2F) Reference example 1 · 1 H-NMR (400MHz, solvent: deuterated chloroform), δ(ppm): 8.65(m,2H), 8.45(d,1H), 7.85(t,1H), 7.70(d ,1H), 4.25(t,2H), 3.95(s,2H), 3.30(m,1H), 3.20(s,3H), 1.75(m,2H), 1.010(d,3H) · 19 F-NMR (400MHz, solvent: deuterated chloroform), δ (ppm): -70.6 (s, 3F)

[0116] <Solidification confirmation test> The reaction solution of each Example, Comparative Example, and Reference Example was concentrated by a rotary evaporator, and 20 parts of methanol was added to 1 part of the solution, cooled to -25°C, and the presence or absence of crystal precipitation was confirmed. If crystal precipitation occurred, the solidification was evaluated as "good", and if no crystal precipitation occurred, the solidification was evaluated as "bad". The results are shown in Table 1.

[0117] <Purity verification test (HPLC)> The reaction solutions of the Examples, Comparative Examples, and Reference Examples were subjected to HPLC analysis under the following conditions. The purity of the compounds contained was calculated from the peak area ratios obtained by HPLC analysis, and is shown in Table 1. Model used: Hitachi, Ltd. LaChrom 7000 series or equivalent Developing solution: methanol / water / trifluoroacetic acid = 100 / 10 / 1 (wt) Flow rate: 1.0mL / min Column: GL Sciences ODS-3 (4.6 mm I.D. x 250 mm) Oven temperature: 40℃ Measurement wavelength: 254nm Sample injection volume: 10 μL

[0118] [Table 1]

[0119] From Table 1, it was found that, as in Reference Example 1, when Rf in the general formula (1) corresponds to PFAS, the compound is solidified, but as in Comparative Example 1, when Rf in the general formula (1) does not correspond to PFAS, the compound is not solidified. In addition, it was found that the compounds of Examples 1 to 4 can be solidified even though Rf in the general formula (1) is a structure that does not correspond to PFAS. In addition, it was found that in Examples 1 to 4, since solidification is possible, the compound contained in the reaction solution can be obtained with high purity. In particular, it was found that in Examples 1 and 3, the compound contained in the reaction solution can be obtained with higher purity. [Industrial Applicability]

[0120] The compounds of the present invention are useful as semiconductor materials.

Claims

1. A compound represented by the following general formula (1): 【Chemistry 1】 [In formula (1), R １ represents an alkylene group. R ２ represents an optionally substituted alkyl group or a hydrogen atom. Rf represents a phenyl group in which at least one hydrogen atom may be substituted with a fluorine atom. However, R １ is an alkylene group having 2 or more carbon atoms, or R ２ is an alkyl group substituted with an alkoxy group or a hydrogen atom.

2. R １ represents a methylene group or an ethylene group, R ２ The compound according to claim 1 , wherein represents an alkyl group substituted with an alkoxy group.

3. R １ represents an ethylene group; R ２ The compound according to claim 1 , wherein represents an alkyl group which may be substituted with an alkoxy group or a hydrogen atom.

4. The compound according to claim 1 , wherein Rf represents a perfluorophenyl group.

5. A non-ionic photoacid generator (A) comprising the compound according to any one of claims 1 to 4.

6. A resin composition for photolithography (Q), comprising the nonionic photoacid generator (A) according to claim 5.

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